Structural analysis of lignite-derived humic acid and its microscopic interactions with heavy metal ions in aqueous solution.

Understanding heavy metal environmental behavior with humic acid (HA) is critical. There is currently a lack of information on the control of its structure organization on its reactivity to metals. The difference in HA structures under non-homogeneous conditions is critical for revealing its micro-interaction with heavy metals. The heterogeneity of HA was reduced using the fractionation method in this study, the chemical properties of HA fractions were analyzed using py-GC/MS, and the structural units of HA were proposed. Pb2+ was used as a probe to investigate the difference in the adsorption capacity of HA fractions. The microscopic interaction of structures with heavy metal was investigated and validated by structural units. The results show that as molecular weight increased, the oxygen content and the number of aliphatic chains decreased, but the opposite was true for aromatic and heterocyclic rings. The adsorption capacity for Pb2+ was as follows: HA-1 > HA-2 > HA-3. According to the linear analysis of the influencing factors of maximum adsorption capacity and possibility factors, the adsorption capacity was positively correlated with the contents of acid groups, carboxyl groups, phenolic hydroxyl groups, and the number of aliphatic chains. The phenolic hydroxyl group and the aliphatic-chain structure have the greatest impact. Therefore, structural differences and the number of active sites play an important role in adsorption. The binding energy of HA structural units to Pb2+ was calculated. It was found that the chain structure is easier to bind to heavy metals than aromatic rings, and the affinity of-COOH to Pb2+ is greater than that of -OH. These findings can help improve the adsorbent design.

Calcium-doped magnetic humic acid nano particles for the efficient removal of heavy metals from wastewater: the role of Ca.

Ca doping is an effective method for improving the adsorption capacity of HA-Fe aggregates and regulating their structures. Understanding the structural characteristics of Ca-HA-Fe aggregates can help explore their microscopic adsorption effect on heavy metals. However, the heterogeneity of HA results in an incomplete understanding of the structural characteristics of the ternary system of Ca-HA-Fe aggregates and adsorption of the quaternary system of Ca-HA-Fe-Pb/Cu/Cd. In this study, interactions between Ca-HA-Fe ternary and Ca-HA-Fe-Pb/Cu/Cd quaternary systems were discussed from a molecular perspective. The structures of the basic structural units of HA were identified. Density functional theory (DFT) was employed to calculate the stable states of basic structural units of HA and Ca2+. The results showed that hydroxyl and carboxyl groups exhibited the highest capacity to bind with Ca2+. The interactions among Ca, HA, and Fe led to the formation of network aggregates. The binding energies of functional groups for heavy metals and the feasibility of ion exchange were calculated by the method of experiment and DFT. According to the contribution of functional group complexation and ion exchange, the ion exchange values for Pb2+, Cu2+, and Cd2+ were 66.71%, 62.87%, and 60.79%, respectively, which indicated that Ca2+ ion exchange showed considerable potential in enhancing the adsorption capacity of heavy metals.

A Sandwich Structure of Fulvic Acid and PMIDA-Modified LDHs for the Simultaneous Removal of Cu2+ and Aniline in Multicomponent Solutions.

The coexistence of organic and inorganic pollutants in industrial wastewater has emerged as a concerning environmental issue worldwide due to the critical levels of biological toxicity of these pollutants. In this context, the present study proposes a sandwich structure of fulvic acid and PMIDA-modified LDHs (FA/PMIDA-LDHs) for the simultaneous removal of Cu2+ and aniline from wastewater. The specific structure was synthesized using a combination of coprecipitation and impregnation methods. Abundant benzene rings and oxygen-containing functional groups greatly increased the number of sites for the adsorption of both Cu2+ and aniline. The maximum adsorption capacity of Cu2+ and aniline in solution with initial pH 5.0 at 25 °C could reach 221.24 and 132.28 mg/g, respectively. Cu2+ could be chelated by the functional groups in the FA/PMIDA-LDHs structure, and a coupled reduction-complexation mechanism was proposed for this process. The uptake of aniline on FA/PMIDA-LDHs was demonstrated to be a result of the combination of coordination forces, hydrophobic effects, π-π interactions, and hydrogen bonds. In a multicomponent solution, FA/PMIDA-LDHs exhibited excellent salt tolerance of up to 1000 mg/L of Na+ or Ca2+. The effects of Fe3+, Ni2+, Cl-, Cr2O72-, SO42-, and H2PO4- on the uptakes of Cu2+ and aniline were also investigated.

Oxidation of Congo red by Fenton coupled with micro and nanobubbles.

Dye wastewater is a kind of refractory organic wastewater. Fenton coupled with micro-nano bubbles (MNBs+FT) was used for the degradation of Congo red (CR), aiming at simplifying the organic pollutants degradation process and reducing the cost of the process. The optimum condition of Fenton alone, the outlet pressure of the cavitation process and different combinations on the degradation of CR dye wastewater were discussed in this study. The results showed that the degradation of CR (100 mg/L) could reach 94.4% by using the MNBs+FT at the pH of 7, which was 72% higher than that using Fenton oxidation alone and 79% higher than that using MNBs alone. Based on the same degradation efficiency, the traditional Fenton process alone required 8 times the dose of oxidants of these combination systems, and the synergy coefficient of MNBs+FT was up to 2.44. ESR analysis indicated that ·OH was the predominant active species during the degradation of CR and MNBs+FT improved the utilization efficiency of H2O2 and produced more ·OH. Besides, the MNBs+FT could extend the pH range of the high-efficiency oxidation reaction, and it could also keep a high degradation rate under neutral conditions, which eliminated the process of adjusting the pH and reduced the anti-corrosion requirements of the equipment. According to the economic analysis results, the total cost of treatment for the MNBs/FT was about 13% of the cost of only the Fenton process. This study provides a reference for the application of MNBs+FT systems in full-scale dye wastewater treatment.

Remediation of the soil contaminated by heavy metals with nano-hydroxy iron phosphate coated with fulvic acid.

Heavy metals pose a serious threat and damage to ecological health when released into the environment. n-HFP is usually used to remediate soils contaminated with heavy metals, but its ability to solidify heavy metals is limited. FA has good ability to trap heavy metals due to its abundant oxygen-containing functional groups. However, the solubility of FA in water limits its application in the field of heavy metal removal. In this paper, n-HFP@FA was prepared by co-precipitation method. Through FT-IR and BET analysis, the oxygen-containing functional groups and specific surface area of n-HFP@FA increased due to the addition of FA. The adsorption behaviour of n-HFP@FA on Pb, Cd, and Cu followed the pseudo-second-order and Langmuir isotherm models. In addition, the maximum adsorption capacities of n-HFP@FA for Pb, Cd, and Cu were 371.1, 190.5, and 129.75 mg/g, respectively. As shown by FT-IR and XPS analysis, the main mechanisms of Pb, Cd and Cu removal by n-HFP@FA are: complexation, electrostatic and precipitation. The n-HFP@FA showed high removal rates of Pb, Cd, and Cu in soil leachates of different pH. In the soil remediation experiments, the BCR method and Pearson correlation analysis showed that the acid-soluble, reducible and oxidizable fractions of Pb, Cd, and Cu in the soil were effectively converted into a more stable residual fraction. This study opens up a prospect for the application of n-HFP@FA composites in the remediation of contaminated soil.

Calcium-Modified Fe3O4 Nanoparticles Encapsulated in Humic Acid for the Efficient Removal of Heavy Metals from Wastewater.

Ca-modified Fe3O4 nanoparticles encapsulated in humic acid (HA-Ca/Fe3O4) were produced using a co-precipitation method. Furthermore, the adsorption performance of HA-Ca/Fe3O4 as well as the effect of coexisting ions and mechanisms were evaluated. A good description of the adsorption process was given using pseudo-second-order kinetic and Langmuir models. The adsorption capacities of HA-Ca/Fe3O4 for Pb2+, Cu2+, and Cd2+ were 208.33, 98.33, and 99.01 mg g-1, respectively. The 0.02-0.1 times concentrations in alkali and alkaline-earth metals promoted Pb2+ and Cd2+ adsorption; however, any concentration of alkali and alkaline-earth metals inhibited Cu2+-ion adsorption, probably owing to the differences in ionic radii between the interfering and heavy-metal ions. Pb2+, Cu2+, and Cd2+ removal using HA-Ca/Fe3O4 occurred via ion exchange, complexation of O-containing functional groups, mineral precipitation, and π-electron coordination. A method was proposed to calculate the contribution of these mechanisms to the adsorption process. In practice, HA-Ca/Fe3O4 can remove 99% Pb2+ and 91% Cu2+ and Cd2+ from real wastewater samples. Following five adsorption-desorption cycles, HA-Ca/Fe3O4 adsorption capacity did not change significantly. The aforementioned results indicated that HA-Ca/Fe3O4 presented a good potential in removing heavy metals in wastewater.

Characteristics of Moisture Transfer and Surface Crack Development of a Single Lignite Particle Driven by Humidity Difference.

The research on moisture transfer characteristics and surface crack development of a single lignite particle (SLP) driven by humidity difference is helpful to achieve a better understanding of the fragmentation characteristics of lignite during the moisture transfer process. This is of great significance to the safe operation of a drying system. The characteristics of moisture transfer within SLP driven by humidity difference were studied in different stages. Six drying equations commonly used in the literature were selected to describe the moisture transfer behavior. The apparent diffusion coefficient (D eff) of moisture in each stage was calculated to compare the driving forces of moisture transfer in different stages. The surface crack rate (CR) was used to quantitatively analyze the fragmentation characteristics of SLP caused by moisture transfer. The results showed that the moisture transfer process of SLP driven by humidity difference can be divided into three stages, and stage I is the main moisture removal stage. The larger the particle size, the longer the stage I, while less moisture is removed in this stage. A logarithmic drying equation best simulates the moisture transfer process of SLP. The larger the particle size, the larger the D eff value in each stage. The driving force of moisture transfer in stage I is the largest, which is the opposite of a thermal drying process. CR for SLP has experienced a rapid increase - stable at the highest value - rapid decrease - stable during the moisture transfer process driven by the humidity difference.

Preparation of Humic Acid/l-Cysteine-Codecorated Magnetic Fe3O4 Nanoparticles for Selective and Highly Efficient Adsorption of Mercury.

Humic acid and l-cysteine-codecorated magnetic Fe3O4 nanoparticles (HA/LC-MNPs) were synthesized using a coprecipitation method. Humic acid fractions abundant with carboxyl and hydroxyl groups can be selectively coated on the surface of MNPs during synthesis. HA/LC-MNPs with abundant heteroatoms (N, S, and O) show excellent removal capacity, great selectivity, and also fast trapping of Hg2+ in a wide pH range. The adsorption capacity of HA/LC-MNPs for Hg2+ can reach 206.5 mg/g, and the chemisorption was attributed to the major adsorption form. In competitive adsorption, HA/LC-MNPs preferentially adsorbed Hg2+ with an affinity order of Hg2+ > > Pb2+ > Cu2+ ≫ Zn2+ > Cd2+. In total, 93.91% of Hg2+ can be quickly captured in the presence of a 6000 times higher concentration of competing metal ions (Pb2+, Cu2+, Cd2+, and Zn2+) within 30 min. The adsorption mechanism was analyzed using X-ray photoelectron spectroscopy (XPS). It suggested that the HA/LC-MNPs enhanced the adsorption capacity of Hg2+ because of the complexing abilities of the multiple thiol, amino, and carboxyl groups in sorbents with Hg2+, the ion exchange ability of the carboxyl group, and the negative charge surface. All in all, HA/LC-MNPs are a potentially useful and economic material for the selective removal of Hg2+ from polluted water.

Adsorption of direct yellow brown D3G from aqueous solution using loaded modified low-cost lignite: Performance and mechanism.

Low-cost lignite-based, copper-containing adsorbents (Cu-raw) were developed through a simple ultrasonic impregnation protocol for enhanced adsorption of direct yellow brown D3G (DYB) from aqueous solutions while treating copper-containing wastewater. The adsorbent was characterized by X-ray diffraction (XRD), scanning electron microscopy-energy dispersion spectroscopy (SEM-EDS), Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The adsorption isotherms and kinetics were studied, and the factors that affect the adsorption, such as adsorbent dosage and solution pH, were investigated. The results showed that DYB adsorption was highly pH dependent and the isotherm of adsorption could be well described by the Langmuir-Freundlich model and the maximum DYB adsorption capacity was estimated to be 369 mg/g at 25°C. The electrostatic and chelating interactions were the main interfacial interaction mechanism, and the synergetic removal performance of lignite toward cationic metal ions and anionic dye was shown. The kinetic data were well fitted to the pseudo-second-order equation, indicating that chemical sorption was the rate-limiting step. The findings reported in this work highlight the potential of using lignite as an effective low-cost adsorbent for the removal of organic pollutants from wastewater.

Water Clusters in Lignite and Desorption Energy Calculation by Density Functional Theory.

The interaction of water and hydrophilic sites with hydroxyl, carboxyl, and multiple oxygen-containing functional groups (OFGs) in lignite molecules was studied by density functional theory. The adsorption of water molecules on the lignite surface initially resulted in the formation of hydrogen bond-driven stable rings by three to four water molecules, followed by the formation of three-dimensional water clusters like a ″patchwork″. Aqueous layer thickness obtained from the water cluster size was 0.4-0.6 nm, which was consistent with the experimental data. Thus, pore-filling water beyond this range was less affected by the OFGs on the surface. Calculation of the adsorption energy predicts that the water clusters were primarily formed in the hydrophilic sites with three OFGs (site 1, including a carbonyl group, an alcoholic hydroxyl group and an etheroxy group in tetrahydropyran), then in COOH, and in O-H. For isolated hydroxyl groups, the interaction between the hydroxyl group and water molecules was weaker than that between the water molecules. When the water cluster was located at the hydrophilic sites with two or more OFGs, the adsorption energy of lignite-water interaction was higher than that of water-water interaction. Investigating the thermodynamics of the adsorption process at a molecular scale will help in understanding both drying and resorption process of dried lignite during industrial production.